US6913797B1 - Decahydronaphthalene derivative - Google Patents

Decahydronaphthalene derivative Download PDF

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US6913797B1
US6913797B1 US09/763,531 US76353101A US6913797B1 US 6913797 B1 US6913797 B1 US 6913797B1 US 76353101 A US76353101 A US 76353101A US 6913797 B1 US6913797 B1 US 6913797B1
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trans
decahydronaphthalene
group
phenyl
fluoro
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Shinji Ogawa
Hiroyuki Ohnishi
Yutaka Nagashima
Sadao Takehara
Makoto Negishi
Haruyoshi Takatsu
Gerwald Grahe
Rainer Bruno Frings
Christine Fugger
Cornelia Pithart
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DIC Corp
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Dainippon Ink and Chemicals Co Ltd
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Definitions

  • the present invention relates to a decahydronaphthalene derivative, which is a novel liquid crystal compound, and a liquid crystal composition containing said derivative.
  • This derivative is useful as a liquid crystal material for electrooptical liquid crystal display, and has a wide temperature range in particular.
  • Liquid crystal display elements have come to be used in not only clocks and calculators, but also in various types of measuring instruments, automobile instrument panels, word processors, Personal Digital Assistants, printers, computers and televisions.
  • Typical examples of liquid crystal display methods include TN (twisted nematic) types, STN (super twisted nematic) types, DS (dynamic scattering) types, GH (guest host) types and FLC (ferroelectric liquid crystal) types.
  • TN twisted nematic
  • STN super twisted nematic
  • DS dynamic scattering
  • GH guest host
  • FLC ferrroelectric liquid crystal
  • Liquid crystal materials are required to have various characteristics to accommodate these display and driving methods. Although a wide temperature range is extremely important in nearly all cases, this includes that in which the nematic phase upper limit temperature (T N-I ) is sufficiently high, and the melting point (T C-N ) or the smectic-nematic transition temperature (T S-N ) is sufficiently low.
  • T N-I nematic phase upper limit temperature
  • T C-N melting point
  • T S-N smectic-nematic transition temperature
  • V th threshold voltage
  • birefringence ( ⁇ n) is also an important characteristic. Although various values are required according to the display method, a low value is frequently required in the case of liquid crystal devices having a large cell thickness for easy manufacturing.
  • liquid crystal compounds are formed from a central skeleton (core) portion and side groups (side chains and polar groups).
  • core central skeleton
  • side groups side chains and polar groups.
  • ring structure that composes the core portion, such as a 1,4-phenylene group (which may be substituted with fluorine) and trans-1,4-cyclohexylene group, as well as heterocyclic aromatics such as a pyridine-2,5-diyl group and pyrimidne-2,5-diyl group, and saturated heterocyclic rings such as a dioxane-trans-1,4-diyl group and piperidine-1,4-diyl group.
  • this ring structure is practically limited to a 1,4-phenylene group (which may be substituted with fluorine), trans-1,4-cyclohexylene group and a small number of heterocyclic aromatics.
  • liquid crystal compounds composed of these ring structures alone are currently unable to adequately accommodate the characteristics required of increasingly sophisticated liquid crystal compounds.
  • trans-2,6-trans-decahydronaphthalene group are saturated rings that do not contain hetero atoms such as oxygen atoms or nitrogen atoms, in addition to being expected to demonstrate superior stability, they are also expected to improve liquid crystal properties.
  • hetero atoms such as oxygen atoms or nitrogen atoms
  • trans-2,6-trans-decahydronaphthalene derivatives reported thus far (W. Sucrow and H. Wolter, Chimia, 36, 460 (1982); Mol. Cryst. Liq. Cryst., 95, 63 (1983)), and hardly anything is known regarding their characteristics.
  • the problem to be solved by the present invention is to provide a novel liquid crystal composition in the form of a decahydronaphthalene derivative, and to provide a liquid crystal composition suitable for STN or TFT driving that uses any of these derivatives, has a wide nematic phase temperature range, has a low birefringence, and is able to be driven at a low voltage and respond rapidly.
  • the present invention provides a novel liquid crystal compound in the form of a decahydronaphthalene derivative represented by general formula (I).
  • Invention 1 A compound represented by general formula (I): (wherein, R and Z may be substituted with a halogen and represent alkyl groups or alkoxy groups having 1-16 carbon atoms, alkenyl groups having 2-16 carbon atoms, alkenyloxy groups having 3-16 carbon atoms, alkyl groups having 1-12 carbon atoms substituted with an alkoxy group having 1-10 carbon atoms, hydrogen atoms, fluorine atoms, chlorine atoms, trifluoromethoxy groups, difluoromethoxy groups, trifluoromethyl groups, 2,2,2-trifluoroethoxy groups, cyano groups, cyanato groups, hydroxy groups or carboxy groups, m and n may be the same or different and respectively and independently represent an integer of 0-2, m+n 3, L and M may be the same or different and respectively and independently represent —CH 2 CH 2 —, —CH(CH 3 )CH 2 —, —CH 2 CH(CH 3 )—, —CH 2 O
  • Invention 2 A compound described in Invention 1 wherein, ring A and ring B when present respectively and independently represent a 1,4-phenylene group, naphthalene-2,6-diyl group, 1,2,3,4-tetrahydronaphthalene-2,6-diyl group, trans-1,4-cyclohexylene group or decahydronaphthalene-2,6-diyl group that may be substituted with fluorine atom(s).
  • Invention 3 A compound described in Invention 1 wherein, ring A or ring B when present respectively and independently represent a 1,4-phenylene group or trans-1,4-cyclohexylene group that may be substituted with fluorine atom(s).
  • Invention 4 A compound described in Invention 1 wherein, L and M when present represent —CH 2 CH 2 —, —CH 2 O—, —OCH 2 —, —CF 2 O—, —OCF 2 —, —COO—, —OCO—, —CF ⁇ CF— or a single bond.
  • Invention 5 A compound described in Invention 1 wherein, L or M represents a single bond.
  • Invention 6 A compound described in Invention 1 wherein, L and M represent single bonds.
  • Invention 7 A compound described in Invention 1 wherein, 1 ⁇ m+n ⁇ 2.
  • Invention 8 A compound described in Invention 1 wherein, R represents an alkyl group, alkoxy group, alkenyl group or alkenyloxy group having 1-12 carbon atoms.
  • Invention 9 A compound described in Invention 1 wherein Z represents a halogen atom or an alkyl group, alkoxy group, alkenyl group, alkenyloxy group or cyano group having 1-12 carbon atoms.
  • Invention 10 A compound described in Invention 1 wherein, R represents an alkyl group or alkenyl group having 1-12 carbon atoms, m represents 1, n represents 1, ring A represents a trans-1,4-cyclohexylene group, ring B represents a 3-fluoro-1,4-phenylene group or 3,5-difluoro-1,4-phenylene group, L and M represent single bonds, and Z represents a fluorine atom, chlorine atom, trifluoromethoxy group, difluoromethoxy group, trifluoromethyl group, 2,2,2-trifluoroethoxy group or cyano group.
  • Invention 11 A compound described in Invention 1 wherein, R represents an alkyl group or alkenyl group having 1-12 carbon atoms, m represents 0, n represents 1, ring B represents a 3-fluoro-1,4-phenylene group or 3,5-difluoro-1,4-phenylene group, M represents a single bond and Z represents a fluorine atom, chlorine atom, trifluoromethoxy group, difluoromethoxy group, trifluoromethyl group, 2,2,2-trifluoroethoxy group or cyano group.
  • Invention 12 A compound described in Invention 1 wherein, R and Z represent alkyl groups or alkenyl groups having 1-12 carbon atoms, m and n represent 1, rings A and B represent 1,4-phenylene groups or trans-1,4-cyclohexylene groups, and L and M represent single bonds.
  • Invention 13 A compound described in Invention 1 wherein, R and Z represent alkyl groups or alkenyl groups having 1-12 carbon atoms, at least one of R or Z represents an alkenyl group, m represents 1, n represents 0, rings A and B represent 1,4-phenylene groups or trans-1,4-cyclohexylene groups, and L represents a single bond.
  • Invention 14 A compound represented by general formula (II): (wherein, R 4 represents an alkyl group, alkoxy group, alkenyl group, alkenyloxy group or alkoxyalkyl group, L 1 represents —CH 2 CH 2 —, —CH(CH 3 )CH 2 —, —CH 2 CH(CH 3 )—, —CH 2 O—, —OCH 2 —, —CF 2 O—, —OCF 2 —, —COO—, —OCO—, —CH ⁇ CH—, —CF ⁇ CF—, —C ⁇ C—, —O(CH 2 ) 3 —, —(CH 2 ) 3 O—, —(CH 2 ) 4 — or a single bond, R 4 represents an alkenyl group, alkenyloxy group or alkoxyalkyl group when L 1 represents a single bond, ring A and m are the same as defined in general formula (I), and the decahydronaphthalene ring
  • Invention 15 A production method of general formula (II) described in Invention 14 including: reducing a compound represented by general formula (II-A): (wherein, R 4 is the same as previously defined in general formula (II), ring E represents a 1,4-phenylene group or trans-1,4-cyclohexylene group, L and m are the same as previously defined in general formula (I), and the decahydronaphthalene ring has a trans form), and oxidizing the hydroxyl group as necessary.
  • general formula (II-A) wherein, R 4 is the same as previously defined in general formula (II), ring E represents a 1,4-phenylene group or trans-1,4-cyclohexylene group, L and m are the same as previously defined in general formula (I), and the decahydronaphthalene ring has a trans form
  • Invention 16 A compound represented by general formula (V-1) or general formula (V-2): (wherein, U 1 and U 2 respectively and independently represent an oxygen atom or the following structure: (wherein, k represents an integer from 1 to 7), L is the same as previously defined in general formula (I), and the decahydronaphthalene ring has a trans form).
  • Invention 17 A production method of general formula (V-1) or general formula (V-2) described in Invention 16 including: converting a compound represented by general formula (V-1A) or general formula (V-2A): (wherein, k is the same as previously defined in general formula (V-1) or general formula (V-2), and L is the same as previously defined in general formula (I)) into an enamine using a secondary amine, and reacting it with methyl vinyl ketone to obtain a compound represented by general formula (V-1B) or general formula (V-2B) (wherein, k is the same as previously defined in general formula (V-1) or general formula (V-2), and L is the same as previously defined in general formula (I)) followed by reductive hydrogenation.
  • Invention 18 A production method of general formula (V-1) described in Invention 16 including: reducing a compound represented by formula (V-1C): oxidizing the hydroxyl groups as necessary, and protecting the carbonyl groups as necessary.
  • Invention 19 A production method of general formula (V-2) described in Invention 16 including: reducing a compound represented by general formula (V-2C): (wherein, although ring G represents a cyclohexane ring or benzene ring, a single bond(s) of the cyclohexane ring may be replaced by double bond(s), and although rings F and H respectively and independently represent the following structures: wherein, U 1 is the same as previously defined in general formula (V-1) or general formula (V-2)), a single bond(s) of the cyclohexane ring may be replaced by double bond(s)), oxidizing the hydroxyl group as necessary, and further protecting the carbonyl group as necessary.
  • V-2C general formula (V-2C): (wherein, although ring G represents a cyclohexane ring or benzene ring, a single bond(s) of the cyclohexane ring may be replaced by double bond(s), and although rings F and H
  • Invention 20 A production method of general formula (V-1a): (wherein, k is the same as previously defined in general formula (V-1) or general formula (V-2)), which is one of the structures of general formula (V-1) described in Invention 16, including monoacetalation of a compound represented by general formula (V-1D):
  • Invention 21 A liquid crystal composition containing a compound described in any of Inventions 1 through 13.
  • Invention 22 A liquid crystal device having for its constituent feature the liquid crystal composition described in Invention 21.
  • Invention 23 An active matrix drive, liquid crystal device that uses the liquid crystal composition described in Invention 21.
  • Invention 24 A super twisted nematic liquid crystal device that uses the liquid crystal composition described in Invention 21.
  • a compound of general formula (I) provided in the present invention is preferably of the form described below.
  • R and Z represent alkyl groups or alkoxy groups having 1-16 carbon atoms, alkenyl groups having 2-16 carbon atoms, alkenyloxy groups having 3-16 carbon atoms, alkyl groups having 1-12 carbon atoms substituted with alkoxy group(s) having 1-10 carbon atoms, hydrogen atoms, fluorine atoms, chlorine atoms, trifluoromethoxy groups, difluoromethoxy groups, trifluoromethyl groups, 2,2,2-trifluoroethoxy groups, cyano groups, cyanato groups, hydroxyl groups or carboxyl groups, which may be substituted with halogen(s), a straight chain alkyl group having 1-12 carbon atoms or a straight chain alkenyl group having 2-12 carbon atoms is preferable, a straight chain alkyl group having 1-7 carbon atoms or a straight chain alkenyl group having 2-7 carbon atoms is more preferable, and the following structures are particularly preferable for R in the case
  • Ring A and ring B when present may be the same or different, represent a trans-1,4-cyclohexylene group wherein one CH 2 group or more than one adjacent CH 2 groups in the group may be replaced by —O— or —S—, or a 1,4-phenylene group, 1,4-cyclohexenylene group, 1,4-bicylo(2,2,2)octylene group, piperidine-1,4-diyl group, naphthalene-2,6-diyl group, trans-decahydronaphthalene-trans-2,6-diyl group or 1,2,3,4-tetrahydronaphthalene-2,6-diyl group wherein one CH group or more than one adjacent CH groups in the group may be replaced by —N ⁇ , and although these may be substituted
  • L and M when present may be the same or different, and represent —CH 2 CH 2 —, —CH(CH 3 )CH 2 —, —CH 2 CH(CH 3 )—, —CH 2 O—, —OCH 2 —, —CF 2 O—, —OCF 2 —, —COO—, —OCO—, —CH ⁇ CH—, —CF ⁇ CF—, —C C—, —O(CH 2 ) 3 —, —(CH 2 ) 3 O—, —(CH 2 ) 4 — or a single bond, —CH 2 CH 2 — or a single bond is preferable for L while a single bond is particularly preferable, and —COO—, —OCO—, —CH 2 CH 2 —, —C C— or a single bond is preferable for M, while a single bond is particularly preferable.
  • R is the same as previously defined in formula (I), a straight chain alkyl group having 1-7 carbon atoms or a straight chain alkenyl group of the structure shown below is preferable, and although R 1 represents an alkenyl group having 2-16 carbon atoms, the following structure is preferable): (wherein, the right side is linked to a ring).
  • a compound of general formula (I) can be produced based on the steps indicated below.
  • the production method of the compound of general formula (I) is not limited to the production examples described below.
  • (IA-1) which includes general formula (Iaf) from general formula (Iaa) and general formula (Ibf) from general formula (Iba): (wherein, R 2 , L, Z 1 , Z 2 , Z 3 , Z 4 , ring A and m are the same as previously defined, and decahydronaphthalene ring has a trans form) can be produced.
  • R 2 , L, Z 1 , Z 2 , Z 3 , Z 4 , ring A and m are the same as previously defined, and decahydronaphthalene ring has a trans form
  • (IA-3) which includes general formula (Iao) from general formula (Iaj) and general formula (Ibo) from general formula (Ibj): (wherein, R 2 , L, Z 1 , Z 2 , Z 3 , Z 4 , ring A and m are the same as previously defined, and the decahydronaphthalene ring has a trans form) can be produced.
  • 1-4 Synthesis of General Formula (Iai) from General Formula (Iag), General Formula (Iar) from General Formula (Iap), General Formula (Ibi) from General Formula (Ibg) and General Formula (Ibr) from General Formula (Ibp)
  • XV Organometallic reagent
  • general formula (IA-4) which includes general formula (Iai) from general formula (Iag), general formula (lar) from general formula (Iap), general formula (Ibi) from general formula (Ibg) and general formula (Ibr) from general formula (Ibp): (wherein, R, L, Z 2 , Z 3 , Z 4 , ring A and m are the same as previously defined, M 1 represents a single bond or an alkenyl group having 1-4 carbon atoms, and the decahydronaphthalene ring has a trans form) can be produced.
  • a halogenating agent such as thionyl halide
  • 1-7 Synthesis of General Formula (Idi) from General Formula (Ida)
  • General formula (IA-7) which includes general formula (Idi) from general formula (Ida): (wherein, R 4 , L, Z 1 , Z 3 Z 4 ring A and m are the same as previously defined, Z 2 , Z 3 and Z 4 may be the same or different, and the decahydronaphthalene ring has a trans form), can be produced using the method described in 1-4 and a phenyldecahydronaphthalene derivative represented by general formula (IA-6a) for which the synthesis method has already been described: (wherein, R 4 , L, Z 1 , Z 2 , Z 3 , Z 4 , ring A and m are the same as previously defined, Z 2 , Z 3 and Z 4 may be the same or different, and the decahydronaphthalene ring has a trans form).
  • 1-8 Production of General Formula (Idu) from General Formula (Idm)
  • XXII organometallic reagent
  • X 1 , X 2 , X 3 , X 4 and X 5 respectively and independently represent a hydrogen atom, fluorine atom or chlorine atom, and W and Z 1 are the same as previously defined
  • a decahydronaphthalene derivative represented by general formula (IIa) by then dehydrating in the presence of acid catalyst, hydrogenating the double bond of the octahydronaphthalene ring, and isomerizing in the presence of alkaline catalyst as necessary, (IA-10), which includes general formula (Iff) from general formula (Ifa), general formula (Ifo) from general formula (Ifj) and general formula (Iry) from general formula (wherein, R 2 , L, X 1 , X 2 , X 3 , X 4 , X 5 , Z 1 , ring A and m are the same as previously defined, and the decahydronaphthalene ring has a
  • organometallic reagent (XXVII): (wherein, W, R 2 , L, ring A and m are the same as previously defined, and the decahydronaphthalene ring has a trans form) is prepared, and after reacting this with 1,2,3,4-tetrahydronaphthalene-2-one derivative (XXVIII): (wherein, X 1 , X 2 , X 3 and Z 1 are the same as previously defined), by dehydrating in the presence of acid catalyst to obtain 1,2-dihydronaphthalene derivative followed by hydrogenating the double bond of the 1,2-dihydronaphthalene ring, general formula (IA-12), which includes general formula (Igp) from general formula (Iga): (wherein, R 2 , L, X 1 , X 2 , X 3 , Z 1 1 ring A and m are the same as previously defined, and the deca
  • General formula (IA-13) which includes general formula (Igt) from general formula (Igq): (wherein, R 2 , L, X 1 , X 2 , X 3 , ring A and m are the same as previously defined, and the decahydronaphthalene ring has a trans form), can be produced by using the method described in 1-4 and a phenyldecahydronaphthalene derivative represented by general formula (IA-12a), for which the synthesis method has already been described: (wherein, R 2 , L, X 1 , X 2 , X 3 , ring A and m are the same as previously defined, and the decahydronaphthalene ring has a trans form).
  • 1-14 Synthesis of General Formula (Icl) from General Formula (Icj) and General Formula (Icx) from General Formula (Icv)
  • General formula (IA-15) which includes general formula (Idl) from general formula (Idj): (wherein, R 2 , L, Z 2 , Z 3 , Z 4 , ring A and m are the same as previously defined, and the decahydronaphthalene ring has a trans form), can be produced using the method described in 1-4 and a phenyldecahydronaphthalene derivative represented by general formula (IA-14a), for which the synthesis method has already been described: (wherein, R 2 , L, Z 2 , Z 3 , Z 4 , ring A and m are the same as previously defined, and the decahydronaphthalene ring has a trans form).
  • 1-16 Synthesis of General Formula (Idx) from General Formula (Idv)
  • general formula (IA-16) which includes general formula (Idx) from general formula (Idv): (wherein, R 2 , L, Z 2 , Z 3 , Z 4 , Z, ring A and m are the same as previously defined, the plurality of A may be the same or different, and the decahydronaphthalene ring has a trans form) can be produced using the method described in 1-5.
  • an alkenyl form of general formula (XXXI) can also be produced according to 1-2. 2-3 Synthesis of General Formula (Iow) from General Formula (Ioa), General Formula (Ipe) from General Formula (Ipa), General Formula (Ipi) from General Formula (Ipg) and General Formula (Iqe) from General Formula (Iqb) General formula (XXXII): (wherein, ring A, R 4 , m, n, L, M 1 , Z 2 , Z 3 and Z 4 are the same as previously defined, ring D represents a 1,4-phenylene group or trans-1,4-cyclohexylene group, and the decahydronaphthalene ring has a trans form), which can be produced by the above methods or their combinations, can be obtained.
  • An organometallic reagent is then produced that is prepared by directly iodinating or brominating this, or lithionating with alkyl lithium, and allowing the bromine or iodine to react, followed by reacting with a metal such as magnesium or transmetalating using an organometallic reagent such as alkyl lithium.
  • a metal such as magnesium or transmetalating using an organometallic reagent such as alkyl lithium.
  • general formula (IB-3) which includes general formula (Iow) from general formula (Ioa), general formula (Ipe) from general formula (Ipa), general formula (Ipi) from general formula (Ipg) and general formula (Iqe) from general formula (Iqb): (wherein, ring A, ring D, R 3 , R 4 , l, m, n, L, M 1 , Z 2 , Z 3 and Z 4 are the same as previously defined, and the decahydronaphthalene ring has a trans form), can be produced.
  • thiocarboxylate-O-ester can be produced by reacting the corresponding carboxylate ester (IA-16) with Lawesson's reagent.
  • 3-3 General formula (IC-3): (wherein, l is an integer of 0 or greater, R 4 , L, ring A and m are the same as previously defined, and the decahydronaphthalene ring has a trans form) can be produced by reacting sodium chlorodifluoroacetate with an alkanal derivative (L) to overheating. 4. Synthesis of General Formula (I) Intermediates 4-1 Synthesis of General Formula (II)
  • Formula (V-1D) is obtained by hydrogenating formula (V-1C).
  • General formula (V-1) (wherein, U 1 and U 2 are the same as previously defined) can be produced by acetalation of the carbonyl groups followed by isolation of the diketone, monoacetal and diacetal.
  • 4-3 Synthesis of General Formula (V-2)
  • General formula (LII): (wherein, k is the same as previously defined) is obtained by reacting general formula (XLIV) with general formula (V-1A), dehydrating, de-protecting the resulting compound and reacetalization.
  • General formula (V-2) in which L is a single bond can then be produced by hydrogenating the aromatic ring of this compound and oxidizing or acetalating as necessary.
  • General formula (V-2) in which L is a single bond can then be produced by hydrogenating the aromatic rings of this compound and oxidizing or acetalating as necessary.
  • general formula (LIII) or general formula (LIV): (wherein, k and L are the same as previously defined) is obtained in accordance with the method described above. This compound can be obtained by hydrogenating using the method described above.
  • the compounds represented by general formula (I) exhibit superior co-solubility with other liquid crystal materials, they can be suitably used as materials for liquid crystal display cells in the state of a mixture with other liquid crystal compounds.
  • the compound of (I) can be used in any of the various display methods previously described, they are suited for use in simple matrix driving or active matrix driving TN display elements and STN display elements.
  • compositions provided by the present invention contain at least one type of compound represented by general formula (I) as their first component for as preferable typical examples of nematic liquid crystal compounds that can be used by mixing with a compound represented by general formula (I), they particularly preferably contain at least one type of the second to fourth components indicated below as other components.
  • the second component is a so-called fluorine-based (halogen-based) p type liquid crystal compound that is composed of the compounds indicated in general formulas (A1) through (A3) below.
  • R b represents an alkyl group having 1-12 carbon atoms, these may have a straight chain or methyl or ethyl branched structure, a 3-6 membered ring structure, any arbitrary —CH 2 — present in the group may be replaced by —O—, —CH ⁇ CH—, —CH ⁇ CF—, —CF ⁇ CH—, —CF ⁇ CF— or —C ⁇ C—, and any arbitrary hydrogen atom present in the group may be substituted with a fluorine atom or trifluoromethoxy group.
  • a straight chain alkyl group having 2-7 carbon atoms straight chain 1-alkenyl group having 2-7 carbon atoms, straight chain 3-alkenyl group having 4-7 carbon atoms and an alkyl group having 1-5 carbon atoms in which the terminal is substituted with an alkoxyl group having 1-3 carbon atoms are preferable.
  • the compound may have optical activity or be a racemic mixture in the case asymmetric carbons are formed as a result of branching.
  • Rings A, B and C respectively and independently represent a trans-1,4-cyclohexylene group, trans-decahydronaphthalene-trans-2,6-diyl group, 1,4-phenylene group that may be substituted with one or more fluorine atoms, naphthalene-2,6-diyl group that may be substituted with one or more fluorine atoms, tetrahydronaphthalene-2,6-diyl group that may be substituted with one or more fluorine atoms, 1,4-cyclohexenylene group that may be substituted with a fluorine atom, 1,3-dioxane-trans-2,5-diyl group, pyrimidine-2,5-diyl group or pyridine-2,5-diyl group.
  • trans-1,4-cyclohexylene group trans-decahydronaphthalene-trans-2,6-diyl group, naphthalene-2,6-diyl group that may be substituted with a fluorine atom, or 1,4-phenylene group that may be substituted with 1 or 2 fluorine atoms is preferable.
  • ring A be a trans-1,4-cyclohexylene group in the case ring B is a trans-1,4-cyclohexylene group or trans-decahydronaphthalene-trans-2,6-diyl group
  • rings B and A be trans-1,4-cyclohexylene groups in the case ring C is a trans-1,4-cyclohexylene group or trans-decahydronaphthalene-trans-2,6-diyl group.
  • ring A be a trans-1,4-cyclohexylene group in (A3).
  • L a , L b and L c are connecting groups that respectively and independently represent a single bond, ethylene group (—CH 2 CH 2 —), 1,2-propylene group (—CH(CH 3 )CH 2 — and —CH 2 CH(CH 3 )—), 1,4-butylene group, —COO—, —OCO—, —OCF 2 —, —CF 2 O—, —CH ⁇ CH—, —CH ⁇ CF—, —CF ⁇ CH—, —CF ⁇ CF—, —C ⁇ C— or —CH ⁇ NN ⁇ CH—.
  • a single bond, ethylene group, 1,4-butylene group, —COO—, —OCF 2 —, —CF 2 O—, —CH ⁇ CF— or —C ⁇ C— is preferable, and a single bond or ethylene group is particularly preferable.
  • Ring Z is an aromatic ring that can be represented by general formulas (La) through (Lc) below.
  • Y a through Y j respectively and independently represent a hydrogen atom or fluorine atom.
  • at least one of Y a and Y b be a fluorine atom in (La)
  • at least one of Y d through Y f be a fluorine atom in (Lb)
  • Y d particularly preferably being a fluorine atom.
  • Terminal group P a represents a fluorine atom, chlorine atom, trifluoromethoxy group, difluoromethoxy group, trifluoromethyl group or difluoromethyl group, or an alkoxyl group, alkyl group, alkenyl group or alkenyloxy group having 2 or 3 carbon atoms and substituted by a fluorine atom or more than one fluorine atoms.
  • a fluorine atom, trifluoromethoxy group or difluoromethoxy group is preferable, and a fluorine atoms is particularly preferable.
  • the third component is a so-called cyano-based p type liquid crystal compound, and is composed of the compounds indicated with general formulas (B1) through (B3) below.
  • R c represents an alkyl group having 1-12 carbon atoms, and these may have a straight chain or methyl or ethyl branched structure, a 3-6 membered ring structure, any arbitrary —CH 2 — present in the group may be replaced by —O—, —CH ⁇ CH—, —CH ⁇ CF—, —CF ⁇ CH—, —CF ⁇ CF— or —C ⁇ C—, and any arbitrary hydrogen atom present in the group may be substituted with a fluorine atom or trifluoromethoxy group.
  • a straight chain alkyl group having 2-7 carbon atoms straight chain 1-alkenyl group having 2-7 carbon atoms, straight chain 3-alkenyl group having 4-7 carbon atoms and an alkyl group having 1-5 carbon atoms in which the terminal is substituted with an alkoxyl group having 1-3 carbon atoms are preferable.
  • the compound may have optical activity or be a racemic mixture in the case asymmetric carbons are formed as a result of branching.
  • Rings D, E and F respectively and independently represent a trans-1,4-cyclohexylene group, trans-decahydronaphthalene-trans-2,6-diyl group, 1,4-phenylene group that may be substituted with one or more fluorine atoms, naphthalene-2,6-diyl group that may be substituted with one or more fluorine atoms, tetrahydronaphthalene-2,6-diyl group that may be substituted with one or more fluorine atoms, 1,4-cyclohexenylene group that may be substituted with a fluorine atom, 1,3-dioxane-trans-2,5-diyl group, pyrimidine-2,5-diyl group or pyridine-2,5-diyl group.
  • trans-1,4-cyclohexylene group trans-decahydronaphthalene-trans-2,6-diyl group, naphthalene-2,6-diyl group that may be substituted with a fluorine atom, or 1,4-phenylene group that may be substituted with 1 or 2 fluorine atoms is preferable.
  • ring D be a trans-1,4-cyclohexylene group in the case ring E is a trans-1,4-cyclohexylene group or trans-decahydronaphthalene-trans-2,6-diyl group
  • rings D and E be trans-1,4-cyclohexylene groups in the case ring F is a trans-1,4-cyclohexylene group or trans-decahydronaphthalene-trans-2,6-diyl group.
  • ring D be a trans-1,4-cyclohexylene group in (B3).
  • L d , L e and L f are connecting groups that respectively and independently represent a single bond, ethylene group (—CH 2 CH 2 —), 1,2-propylene group (—CH(CH 3 )CH 2 — and —CH 2 CH(CH 3 )—), 1,4-butylene group, —COO—, —OCO—, —OCF 2 —, —CF 2 O—, —CH ⁇ CH—, —CH ⁇ CF—, —CF ⁇ CH—, —CF ⁇ CF—, —C ⁇ C—, —OCH 2 —, —CH 2 O— or —CH ⁇ NN ⁇ CH—.
  • a single bond, ethylene group, —COO—, —OCF 2 —, —CF 2 O—, —CF ⁇ CF— or —C ⁇ C— is preferable, and a single bond, ethylene group or —COO— is particularly preferable.
  • Ring Y is an aromatic ring that can be represented by general formulas (Ld) through (Lf) below.
  • Y k through Y q respectively and independently represent a hydrogen atom or fluorine atom.
  • Y n and Y o are preferably hydrogen atoms in (Le).
  • terminal group P b represents a cyano group (—CN—), cyanato group (—OCN—) or —C ⁇ CCN, a cyano group is preferable.
  • the fourth component is a non-polar liquid crystal having dielectric anisotropy of near 0, and is composed of the compounds indicated with general formulas (C1) through (C3) below.
  • R d and P e respectively and independently represent an alkyl group having 1-12 carbon atoms, and these may have a straight chain or methyl or ethyl branched structure, a 3-6 membered ring structure, any arbitrary —CH 2 — present in the group may be replaced by —O—, —CH ⁇ CH—, —CH ⁇ CF—, —CF ⁇ CH—, —CF ⁇ CF— or —C ⁇ C—, and any arbitrary hydrogen atom present in the group may be substituted with a fluorine atom or trifluoromethoxy group.
  • a straight chain alkyl group having 1-7 carbon atoms, straight chain 1-alkenyl group having 2-7 carbon atoms, straight chain 3-alkenyl group having 4-7 carbon atoms and an alkyl group having 1-5 carbon atoms in which the terminal is substituted with an alkoxyl group having 1-3 carbon atoms are preferable. Moreover, it is more preferable that at least one of these represent a straight chain alkyl group having 1-7 carbon atoms, a straight chain 1-alkenyl group having 2-7 carbon atoms, or a straight chain 3-alkenyl group having 4-7 carbon atoms.
  • Rings G, H, I and J respectively and independently represent a trans-1,4-cyclohexylene group, trans-decahydronaphthalene-trans-2,6-diyl group, 1,4-phenylene group that may be substituted with one or two fluorine atoms, naphthalene-2,6-diyl group that may be substituted with one or more fluorine atoms, tetrahydronaphthalene-2,6-diyl group that may be substituted with one or two fluorine atoms, 1,4-cyclohexenylene group that may be substituted with one or two fluorine atoms, 1,3-dioxane-trans-2,5-diyl group, pyrimidine-2,5-diyl group or pyridine-2,5-diyl group.
  • each compound there be no more than one trans-decahydronaphthalene-trans-2,6-diyl group, naphthalene-2,6-diyl group that may be substituted with one or more fluorine atoms, tetrahydronaphthalene-2,6-diyl group that may be substituted with one or two fluorine atoms, 1,4-cyclohexenylene group that may be substituted with a fluorine atom, 1,3-dioxane-trans-2,5-diyl group, pyrimidine-2,5-diyl group or pyridine-2,5-diyl group, and that the other rings be a trans-1,4-cyclohexylene group or a 1,4-phenylene group that may be substituted with 1 or 2 fluorine atoms or methyl groups.
  • L g , L h and L i are connecting groups that respectively and independently represent a single bond, ethylene group (—CH 2 CH 2 —), 1,2-propylene group (—CH(CH 3 )CH 2 — and —CH 2 CH(CH 3 )—), 1,4-butylene group, —COO—, —OCO—, —OCF 2 —, —CF 2 O—, —CH ⁇ CH—, —CH ⁇ CF—, —CF ⁇ CH—, —CF ⁇ CF—, —C ⁇ C— or —CH ⁇ NN ⁇ CH—.
  • a single bond, ethylene group, —COO—, —OCF 2 —, —CF 2 O—, —CF ⁇ CF— or —C ⁇ C— is preferable, and a single bond, ethylene group, 1,4-butylene group, —COO—, —OCO—, —OCF 2 —, —CF 2 O—, —CF ⁇ CF—, —C—C— or —CH ⁇ NN ⁇ CH— is particularly preferable.
  • More preferable forms in (C1) can be represented by general formulas (C1a) through (C1h) below.
  • R f and P g respectively and independently represent a straight chain alkyl group having 1-7 carbon atoms, straight chain 1-alkenyl group having 2-7 carbon atoms, straight chain 3-alkenyl group having 4-7 carbon atoms, straight chain alkoxyl group having 1-3 carbon atoms or a straight chain alkyl group having 1-5 carbon atoms in which the terminal is substituted with an alkoxyl group having 1-3 carbon atoms.
  • at least one of these represents a straight chain alkyl group having 1-7 carbon atoms, straight chain 1-alkenyl group having 2-7 carbon atoms or straight chain 3-alkenyl group having 4-7 carbon atoms.
  • Rings G1 and H1 respectively and independently represent a trans-1,4-cyclohexylene group, trans-decahydronaphthalene-trans-2,6-diyl group, 1,4-phenylene group that may be substituted with one or two fluorine atoms, naphthalene-2,6-diyl group that may be substituted with one or more fluorine atoms, tetrahydronaphthalene-2,6-diyl group that may be substituted with one or two fluorine atoms, 1,4-cyclohexenylene group that may be substituted with one or two fluorine atoms, 1,3-dioxane-trans-2,5-diyl group, pyrimidine-2,5-diyl group or pyridine-2,5-diyl group.
  • each compound there be no more than one trans-decahydronaphthalene-trans-2,6-diyl group, naphthalene-2,6-diyl group that may be substituted with one or more fluorine atoms, tetrahydronaphthalene-2,6-diyl group that may be substituted with one or two fluorine atoms, 1,4-cyclohexenylene group that may be substituted with a fluorine atom, 1,3-dioxane-trans-2,5-diyl group, pyrimidine-2,5-diyl group or pyridine-2,5-diyl group, and that the other rings in this case be a trans-1,4-cyclohexylene group or a 1,4-phenylene group that may be substituted with 1 or 2 fluorine atoms or methyl groups.
  • Rings G2 and H2 respectively and independently represent a trans-1,4-cyclohexylene group, trans-decahydronaphthalene-trans-2,6-diyl group, 1,4-phenylene group that may be substituted with one or two fluorine atoms or methyl groups, naphthalene-2,6-diyl group that may be substituted with one or more fluorine atoms, or tetrahydronaphthalene-2,6-diyl group that may be substituted with one or two fluorine atoms.
  • each compound there be no more than one trans-decahydronaphthalene-trans-2,6-diyl group, naphthalene-2,6-diyl group that may be substituted with one or more fluorine atoms or tetrahydronaphthalene-2,6-diyl group that may be substituted with one or two fluorine atoms, and that the other rings in this case be a trans-1,4-cyclohexylene group or a 1,4-phenylene group that may be substituted with one or two fluorine atoms or methyl groups.
  • Rings G3 and H3 respectively and independently represent a 1,4-phenylene group that may be substituted with one or two fluorine atoms or methyl groups, naphthalene-2,6-diyl group that may be substituted with one or more fluorine atoms or tetrahydronaphthalene-2,6-diyl group that may be substituted with one or two fluorine atoms.
  • naphthalene-2,6-diyl group that may be substituted with one or more fluorine atoms or tetrahydronaphthalene-2,6-diyl group that may be substituted with one or two fluorine atoms.
  • rings G1, G2, G3, H1, H2 and H3 are the same as previously defined, and ring I1 is the same as ring G1, ring I2 is the same as ring G2 and ring I3 is the same as ring G3.
  • each compound there be no more than one trans-decahydronaphthalene-trans-2,6-diyl group, naphthalene-2,6-diyl group that may be substituted with one or more fluorine atoms, tetrahydronaphthalene-2,6-diyl group that may be substituted with one or two fluorine atoms, 1,4-cyclohexenylene group that may be substituted with a fluorine atom, 1,3-dioxane-trans-2,5-diyl group, pyrimidine-2,5-diyl group or pyridine-2,5-diyl group, and that the other rings in this case be a trans-1,4-cyclohexylene group or a 1,4-phenylene group that may be substituted with one or two fluorine atoms or methyl groups.
  • rings G1, G2, H1, H2, I1 and I2 are the same as previously defined, and ring J1 is the same as ring G1 or ring J2 is the same as ring G2.
  • ring J1 is the same as ring G1 or ring J2 is the same as ring G2.
  • the mixture was cooled in a water bath, and 150 ml toluene solution of 89 ml of methyl vinyl ketone was added dropwise over a period of 2 hours at 20° C. or less. After the dropwise addition was completed, the temperature was increased over a period of 2 hours to reach the reflux temperature.
  • the solution was cooled to room temperature, and a buffer solution of pH 5 which was prepared from B5.2 g of sodium acetate, 104.2 ml of acetic acid, and 104.2 ml of water was added. Reflux was further continued for 5 hours.
  • the organic phase was separated and rinsed with water and a saturated saline solution. The organic phase was dried on anhydrous sodium sulfate. The solvent was evaporated, and 313 g of 6-(trans-4-propylcyclohexyl)-4,4a,5,6,7,8-hexahydro-2(3H)-naphthalenone was obtained.
  • the organic phase was separated and rinsed with water and a saturated saline solution.
  • the organic phase was dried on anhydrous sodium sulfate.
  • the aqueous phase was extracted with 100 ml of hexane, and the extracts were combined with the organic phase.
  • the combined organic phase was rinsed with water, a saturated aqueous solution of sodium hydrogencarbonate, and a saturated saline solution, and dried on anhydrous sodium sulfate.
  • the solvent was evaporated, and 100 ml of toluene and 2.0 g of p-toluenesulfonic acid monohydrate were added.
  • the mixture was heated at 110° C. with stirring while evaporated water was separated and removed. When the evaporation of water was stopped, the temperature was reduced to room temperature. 50 ml of water was added, and the organic phase was separated.
  • the organic phase was rinsed with a saturated aqueous solution of sodium hydrogencarbonate, water and a saturated saline solution, and dried on anhydrous sodium sulfate.
  • the solvent was evaporated, and the whole amount of the residue was dissolved in 200 ml of ethyl acetate.
  • 2.5 g of palladium-carbon (5%, wet) was added, and the mixture was stirred in an autoclave in hydrogen under a pressure of 400 KPa.
  • the solution was added again dropwise to a 60 ml THF solution of 13.5 g of methoxymethyltriphenylphosphonium chloride and 5.5 g of potassium t-butoxide, which has been cooled. The temperature was reduced to room temperature. After the mixture was stirred for 4 hours, water and hexane were added, and the organic phase was separated. After the organic phase was rinsed with water, the solvent was evaporated. 13.6 g of the solid substance obtained was dissolved in 70 ml of THF. 70 ml of 10% hydrochloric acid was added to the solution, and the mixture was stirred for 2 hours. The temperature was reduced to room temperature, water was added to the mixture, and the mixture was extracted with ethyl acetate.
  • the organic phase was separated, rinsed with water, and dried on anhydrous sodium sulfate. Then, the solvent was evaporated. 9.1 g of the oily substance obtained was dissolved in 50 ml of toluene. 2.5 g of sodium benzenesulfinate and 10 ml of 10% hydrochloric acid were added to the solution, and the mixture was heated under refluxing for 20 hours. The temperature was reduced to room temperature. The organic phase was extracted using toluene, rinsed with a saturated aqueous solution of sodium hydrogen carbonate and a saturated saline solution, in sequence, and dried on anhydrous sodium sulfate. Then, the solvent was evaporated.
  • the aqueous phase was extracted with 100 ml of hexane, and the extracts were combined with the organic phase.
  • the combined organic phase was rinsed with water, a saturated aqueous solution of sodium hydrogencarbonate, and a saturated saline solution, and dried on anhydrous sodium sulfate.
  • the solvent was evaporated, and 105 ml of toluene and 1.7 g of p-toluenesulfonic acid monohydrate were added.
  • the mixture was heated at 110° C. with stirring while evaporated water was separated and removed. When the evaporation of water was stopped, the temperature was reduced to room temperature. 50 ml of water was added, and the organic phase was separated.
  • the organic phase was rinsed with a saturated aqueous solution of sodium hydrogencarbonate, water and a saturated saline solution, and dried on anhydrous sodium sulfate.
  • the solvent was evaporated, and the whole amount of the residue was dissolved in 100 ml of ethyl acetate. 3.0 g of carbon with 5% palladium was added, and the mixture was stirred in an autoclave in hydrogen under a pressure of 400 KPa. After stirring for 5 hours at room temperature, the catalyst was removed by way of filtration through celite, and the solvent was evaporated to obtain a trans/cis mixture of trans-6-propyl-2-(3,5-difluorophenyl)-trans-decahydronaphthalene.
  • the organic phase was rinsed with water and a saturated saline solution, and dried on anhydrous sodium sulfate.
  • the solvent was evaporated, and the whole amount of the residue was dissolved in 170 ml of 1,2-dichloroethane. 8.1 ⁇ g of thionyl chloride and 0.1 ml of pyridine were added, and the mixture was stirred for 5 hours.
  • the solvent was evaporated, and the whole amount of the residue was dissolved in 100 ml of dichloromethane. Ammonia gas was injected into the solution while stirring. Two hours later, the solution was filtered.
  • the residue was dissolved in 100 ml of DMF, and 7.9 g of oxalyl chloride was added dropwise.
  • trans-2-propyl-trans-6-(3-fluoro-4-methoxyphenyl)-trans-decahydronaphthalene (which is a compound obtained in a manner similar to (1-a) except that 1-bromo-3-fluro-4-methoxybenzene was used instead of 1-bromo-3,5-difluorobenzene) was added to a mixture of 100 ml of acetic acid and 100 ml of 48% aqueous solution of hydrobromic acid, and the mixture was heated for 20 hours under refluxing. The temperature was reduced to room temperature. Water and toluene were added to the mixture, and the organic phase was separated.
  • the organic phase was rinsed with a saturated aqueous solution of sodium hydrogencarbonate, water, and a saturated saline solution, and dried on anhydrous sodium sulfate.
  • the solvent was evaporated, and the whole amount of the residue was dissolved in 100 ml of dichloromethane. 19.7 g of trifluromenthanesulfonic anhydride was added to the solution, and the mixture was cooled to 5° C. While the mixture was stirred forcefully, 12 ml of pyridine was added dropwise, and thereafter the mixture was further stirred for 1 hour. Water was added to stop the reaction.
  • the organic phase was separated out, and the aqueous phase was extracted with dichloromethane.
  • a 100 ml THF solution of 24 g of 6-propyl-trans-decahydro-2-naphthalenone was added dropwise to a Wittig reagent prepared from 38 g of methoxymethyltriphenylphosphonium chloride and 14 g of potassium t-butoxide in 200 ml of THF, while the mixture was cooled 10° C. or lower. The temperature was reduced to room temperature. After the mixture was stirred for 4 hours, water and hexane were added. The organic phase was separated and rinsed with water, and the solvent was evaporated. The pale yellow oily substance obtained was dissolved in 180 ml of THF. 180 ml of 10% hydrochloric acid was added to the solution, and the mixture was heated for 3 hours under refluxing.
  • the pale yellow solid substance obtained was dissolved in 160 ml of methanol. 20 ml of 10% aqueous solution of sodium hydroxide was added to the solution while cooling the solution to 10° C. or lower. After stirring the mixture for 2 hours, the temperature was reduced to room temperature, and the solvent was evaporated. The pale yellow solid substance obtained was rinsed with water, and recrystallized from a hexane solution to obtain 18 g of white solid 6-propyl-trans-decahydronaphthalene-2-carbaldehyde.
  • trans-decahydronaphthalen-2,6-dione monoethyleneacetal was dissolved in 110 ml of toluene. 50 ml of formic acid was added to the solution, and the mixture was stirred for 1 hour at room temperature. Water was added to the mixture, and the organic phase was separated, rinsed with water, a saturated aqueous solution of sodium hydrogencarbonate, and a saturated saline solution, in sequence, and dried on anhydrous sodium sulfate. Then, the solvent was evaporated to obtain 16 g of pale yellow solid trans-decahydronaphthalen-2,6-dione.
  • the pale yellow solid substance obtained was suspended in 60 ml of 1,2-dichloroethane. 2 g of thionyl chloride, 0.1 ml of pyridine, and 1 ml of DMF were added to the suspension, and the mixture was stirred for 1 hour at room temperature. The solvent was evaporated, and the yellow oily substance obtained was dissolved in 150 ml of dichloromethane. Ammonia gas was injected into the solution while cooling the solution to 10° C. or lower until saturation. After stirring for 1 hour at room temperature, the solvent was evaporated. The yellowish brown solid substance obtained was suspended in 50 ml of DMF. 2 ml of phosphorus oxychloride was added to the suspension while cooling the suspension to 10° C.
  • Trans-6-(4-methoxyphenyl)-trans-2-vinyldecahydronaphthalene obtained in a manner similar to that in Example 1 was dissolved in glacial acetic acid. A 47% aqueous solution of hydrobromic acid was added to the solution, and the mixture was heated for 20 hours under refluxing. The mixture was cooled to room temperature, and water was added to the mixture. Extraction was carried out using toluene, and the organic phase was rinsed with water and then dried on anhydrous sodium sulfate. Then, the solvent was evaporated. The oily substance obtained, which was trans-6-(4-hydroxyphenyl)-trans-2-vinyldecahydronaphthalene, was dissolved in methylene chloride.
  • Trifluoromethanesulfonic anhydride was added dropwise to the solution while cooling the mixture at 10° C. or lower. Subsequently, pyridine was added dropwise, and the mixture was stirred for 1 hour. Water was added, and the mixture was left to stand until the temperature reached room temperature. Then, extraction was carried out using ethyl acetate, and the organic phase was rinsed with water and then dried on anhydrous sodium sulfate. Then, the solvent was evaporated. The oily substance obtained, which was trifluoromethanesulfonate, was dissolved in THF. Dibromobis(diphenylphosphinoethane)nickel(II) and triphenylphosphine were added to the solution.
  • a Grignard reagent prepared from 3-butenyl bromide (1-bromo-3-butene) was added dropwise to the mixture, and the mixture was heated for 16 hours under refluxing. The mixture was left to stand until the temperature reached room temperature. Then, 10% hydrochloric acid was added to the mixture, and the organic phase was extracted using ethyl acetate, rinsed with water, and dried on anhydrous sodium sulfate. After the solvent was evaporated, the residue was purified by silica gel column chromatography (hexane) and recrystallized (ethanol) to obtain white solid trans-6-[4-(3-butenyl)phenyl]-trans-2-vinyldecahydronaphthalene.
  • a THF solution of trans-6-(4-hydroxyphenyl)-trans-2-vinyldecahydronaphthalene obtained by the method disclosed in Example 7 was added dropwise to a suspension of sodium hydroxide in THF, the suspension being cooled to 10° C. or lower. After stirring for 30 minutes at room temperature, a THF solution of 2-propenyl bromide (1-bromo-2-propene) was added dropwise, and the mixture was heated for 1 hour under refluxing. The mixture was left to stand until the temperature reached room temperature, and extraction was carried out using toluene. The organic phase was rinsed with a saturated saline solution and then dried on anhydrous sodium sulfate.
  • Trans-2-(4-carboxy-3-fluorophenyl)-trans-6-vinyldecahydronaphthalene obtained in a manner similar to that in Example 6, dicyclohexylcarbodiimide, and N,N-dimethyl-4-aminopyridine were dissolved in methylene chloride. To this solution, a methylene chloride solution of 2-propenol was added dropwise. After the mixture was stirred for 20 hours at room temperature, the mixture was filtered, and solvent was evaporated.
  • a 120 ml dichloromethane solution of 25 g of trifluoromethanesulfonic anhydride was added dropwise to a 100 ml dichloromethane solution of 24 g yellow crystals of 6-(trans-6-propyl-trans-3,4,4a,5,6,7,8,8a-octahydronaphthalen-2-yl)-2-naphthol, which were obtained in (30-c), while the solution was cooled at 0°. Subsequently, a 70 ml dichloromethane solution of 14 g of pyridine was added dropwise.
  • a Grignard reagent prepared from 1.5 g of metal magnesium and 9 g of 4-bromo-1-butene was added dropwise to a 130 ml THF solution of 25 g of 2-(6-trifluoromethanesulfonyloxynaphthalen-2-yl)-trans-6-propyl-trans-decahydronaphthalene, which was obtained in (30-d), and 0.8 g of dichlorobis(diphenylphosphinoethane)nickel(II), the solution being cooled to 10° C. or lower. The temperature was reduced to room temperature, and the mixture was stirred for 6 hours.
  • the oily substance obtained was dissolved in 140 ml of toluene. 4 g of p-toluenesulfonic acid monohydrate was added to the solution, and the mixture was heated for 4 hours under refluxing using an apparatus equipped with a water separator until evaporation of water stopped. Then, 4 g of p-toluenesulfonic acid monohydrate and 12 g of ethylene glycol was further added, and the mixture was further heated for 4 hours under refluxing until evaporation of water stopped. The solution was cooled to room temperature.
  • the organic phase was separated, rinsed with an aqueous solution of sodium hydrogen sulfite, water, a saturated aqueous solution of sodium hydrogencarbonate, water, and a saturated saline solution, in sequence, and dried on anhydrous sodium sulfate.
  • the solvent was evaporated to obtain 13 g of yellow solid 2-(3,5-difluoro-4-iodophenyl)-6-ethoxy-trans-decahydronaphthalene.
  • the pale yellow solid substance obtained was rinsed with water and recrystallized from a hexane solution to obtain 11 g of pale yellow solid 6-(4-bromophenyl)-trans-decahydronaphthalene-2-carbaldehyde.
  • reaction of 7 g of 2-(4-bromophenyl)-6-(3-oxopropyl)-trans-decahydronaphthalene was carried out to obtain 6 g white crystals of 2-(4-bromophenyl)-6-(3-butenyl)-trans-decahydronaphthalene.
  • reaction of 15 g of 4-(6-oxo-trans-octahydronaphthalen-2-yl)cyclohexanone monoethyleneacetal with a Grignard reagent prepared from 3,4,5-trifluoro-1-bromobenzene, dehydration, and re-acetalization were carried out to obtain 18 g of pale yellow solid 4-[2-(3,4,5-trifluorophenyl)-trans-3,4,4a,5,6,7,8,8a-octahydronaphthalen-6-yl]cyclohexanone ethyleneacetal.
  • reaction of 7 g of 6-(trans-4-propylcyclohexyl)-trans-decahydronaphthalene with a Grignard reagent prepared from 1,2-difluoro-6-bromonaphthalene and dehydration were carried out to obtain 9 g of pale yellow solid 6-(1,2-difluoronaphthalen-6-yl)-2-(trans-4-propylcyclohexyl)-trans-3,4,4a,5,6,7,8,8a-octahydronaphthalene.
  • the versatile host liquid crystal (H-A) was prepared. This host liquid crystal (H-A) exhibits a nematic phase at 116.7° C. or less, and its melting point is 11° C.
  • the physical property values at 20° C. of the threshold voltage (Vth) of a TN cell (cell thickness: 6 ⁇ m) prepared using this composition were as shown below.
  • Comparative liquid crystal composition (HR-1) was prepared comprised of 20% of cyclohexylbenzene derivative (R-1): used in place of (I-3) in Example 1, and 80% of host liquid crystal (H-A).
  • the nematic phase upper limit temperature (T N-I ) of this composition decreased considerably to 70° C.
  • the nematic phase upper limit temperature of (R-1) alone as extrapolated from this was ⁇ 100° C. or below.
  • liquid crystallinity is considerably lower than (I-3).
  • Liquid crystal composition (H-2) was prepared comprised of 20 wt % of (I-18) in Table 3, which is a compound of the present invention: and 80 wt % of host liquid crystal (H-A).
  • the physical property values of (H-2) and the photoelectric characteristic values of a liquid crystal device prepared in the same manner using (H-2) were as shown below.
  • T N-I nematic phase upper limit temperature
  • T C-N melting point
  • Vth threshold voltage
  • a comparative liquid crystal composition (HR-2) was prepared comprised of 20 wt % of phenylbicyclohexane derivative (R-2): which, although having a similar structure to (I-18), the trans-decahydronaphthalene group is substituted with a cyclohexane-4,4′-diyl group, and 80 wt % of host liquid crystal (H-A).
  • R-2 phenylbicyclohexane derivative
  • H-A host liquid crystal
  • melting point also rose 13° C. higher than the host liquid crystal, indicating that the solubility of the compound of (R-2) relative to the host liquid crystal is not that good.
  • the compound of (I-18) of the present invention has effects that are superior to those of compounds of the prior art in terms of preparing a liquid crystal composition that has a wide temperature range, low threshold voltage and allows high-speed response.
  • H-B Versatile n type host liquid crystal
  • a liquid crystal composition (H-3) was prepared comprised of 80% of host liquid crystal (H-B) and 20% of compound (I-9): obtained in Example 10. Its physical property values and photoelectric characteristic values measured with a liquid crystal device prepared in the same manner were as shown below.
  • the threshold voltage (Vth) is a little higher as compared with (H-B), the nematic phase upper limit temperature is more than 10° C. higher, and response is also improved, although only slightly.
  • this (H-3) was allowed to stand for 2 weeks at ⁇ 20° C., liquid crystal precipitation or phase separation was not observed.
  • Nematic liquid crystal composition (H-R 3 ) was prepared by adding 20% of 3-fluoro-4-cyanobenzene derivative (R-3): having a structure in place of (I-9) in Example 40 in which the trans-decahydronaphthalene group is substituted with a cyclohexylene group, to (H-B).
  • R-3 3-fluoro-4-cyanobenzene derivative
  • Example 40 in which the trans-decahydronaphthalene group is substituted with a cyclohexylene group
  • Liquid crystal composition (H-4) was prepared comprised of 80 wt % of (H-A) and 20 wt % of compound (I-23) of the present invention obtained in Example 22:
  • the T N-I of this composition was 116.4° C. Although this (H-4) was allowed to stand for 4 weeks at ⁇ 20° C., crystal precipitation or phase separation was not observed.
  • this composition was crystallized by allowing to stand after cooling to ⁇ 60° C. followed by measurement of T C-N , it was found to be ⁇ 3° C., indicating that it can be made to be significantly lower than (H-A), and that (I-23) dissolves easily in the host liquid crystal.
  • (H-4) was filled into a TN cell having a cell thickness of 6.0 ⁇ m to prepare a liquid crystal device. Measurement of its photoelectric characteristics at 20° C. yielded the values indicated below.
  • ⁇ n The value of ⁇ n was able to be lowered while holding the decrease in T N-I to 4° C. by adding 20 wt % of (I-23). In addition, there are hardly any changes in Vth and ⁇ , and the increase in ⁇ was able to be held to roughly 5 msec.
  • Nematic liquid crystal composition (H-R 4 ) was prepared by adding the same amount (20 wt %) of compound (R-4): in place of (I-23) in Example 41, which although having a similar structure, has a trans-1,4-cyclohexylene group for the ring structure that composes the core, to (H-A).
  • a liquid crystal device was prepared in the same manner, and the photoelectric characteristic values of this composition were as shown below.
  • (H-R 4 ) has a lower value of T N-I than (H-4) and a narrower nematic phase temperature range.
  • the ⁇ n of (H-R 4 ) is larger than (H-4), ⁇ , Vth and ⁇ are essentially no different from (H-4), and response is better than (H-4).
  • Liquid crystal composition (M) was prepared composed of the components listed below.
  • Liquid crystal composition (M-I) was prepared comprised of 3% of (I-10): obtained in Example 9, 3% of (I-9): obtained in Example 10, and 4% of (I-3): obtained in Example 1.
  • the T N-I of this (M-I) was 70.4° C., and ⁇ n was 0.136.
  • the novel decahydronaphthalene derivative of the present invention can be produced industrially extremely easily as shown in the examples, and by adding a small amount to a base liquid crystal, it is possible to have effects that expand the nematic phase temperature range, thereby improving its various characteristics as a nematic liquid crystal. Moreover, the novel decahydronaphthalene derivative of the present invention also has superior co-solubility with base liquid crystals generally used at present. Thus, it is suitable for various types of liquid crystal devices requiring a wide operating temperature range, and is extremely useful as a liquid crystal material.

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Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0047817A2 (de) 1980-08-14 1982-03-24 F. HOFFMANN-LA ROCHE & CO. Aktiengesellschaft Hydrierte Naphthaline, deren Herstellung und Verwendung sowie derartige Naphthaline enthaltende Gemische
DE3150312A1 (de) 1980-12-23 1982-07-22 F. Hoffmann-La Roche & Co. AG, 4002 Basel Decaline, verfahren zu ihrer herstellung und ihre verwendung
JPS57130929A (en) 1980-12-23 1982-08-13 Hoffmann La Roche Decalins
GB2112387A (en) 1981-12-08 1983-07-20 Merck Patent Gmbh Liquid crystal alkyl perhydrophenanthrenes
JPS59141527A (ja) 1983-02-01 1984-08-14 Chisso Corp 部分還元されたナフタリン誘導体
JPS6474270A (en) 1987-09-16 1989-03-20 Mitsui Toatsu Chemicals Dichroic pigment for liquid crystal display
EP0344557A2 (de) 1988-06-01 1989-12-06 F. Hoffmann-La Roche Ag Flüssigkristallkomponenten mit einer Trimethylenoxygruppe
JPH07310048A (ja) 1994-03-25 1995-11-28 Chisso Corp ワニス組成物
US5907005A (en) 1994-03-25 1999-05-25 Chisso Corporation Varnish composition

Patent Citations (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0047817A2 (de) 1980-08-14 1982-03-24 F. HOFFMANN-LA ROCHE & CO. Aktiengesellschaft Hydrierte Naphthaline, deren Herstellung und Verwendung sowie derartige Naphthaline enthaltende Gemische
US4432885A (en) 1980-12-23 1984-02-21 Hoffmann-La Roche Inc. Decalins
DE3150312A1 (de) 1980-12-23 1982-07-22 F. Hoffmann-La Roche & Co. AG, 4002 Basel Decaline, verfahren zu ihrer herstellung und ihre verwendung
JPS57130929A (en) 1980-12-23 1982-08-13 Hoffmann La Roche Decalins
US4434073A (en) 1981-12-08 1984-02-28 Merck Patent Gesellschaft Mit Beschrankter Haftung Perhydrophenanthrene derivatives, their preparation, and their use in liquid-crystalline dielectrics and electro-optical display elements
DE3148448A1 (de) 1981-12-08 1983-07-28 Merck Patent Gmbh, 6100 Darmstadt "perhydrophenanthrenderivate, verfahren zu ihrer herstellung, diese enthaltende fluessigkristalline dielektrika und elektrooptisches anzeigeelement"
GB2112387A (en) 1981-12-08 1983-07-20 Merck Patent Gmbh Liquid crystal alkyl perhydrophenanthrenes
JPS59141527A (ja) 1983-02-01 1984-08-14 Chisso Corp 部分還元されたナフタリン誘導体
JPS6474270A (en) 1987-09-16 1989-03-20 Mitsui Toatsu Chemicals Dichroic pigment for liquid crystal display
EP0344557A2 (de) 1988-06-01 1989-12-06 F. Hoffmann-La Roche Ag Flüssigkristallkomponenten mit einer Trimethylenoxygruppe
JPH0225440A (ja) 1988-06-01 1990-01-26 F Hoffmann La Roche Ag 新規化合物及び液晶混合物
US5238600A (en) 1988-06-01 1993-08-24 Hoffmann-La Roche Inc. Ibimethylenoxy containing liquid crystal compounds
JPH07310048A (ja) 1994-03-25 1995-11-28 Chisso Corp ワニス組成物
US5907005A (en) 1994-03-25 1999-05-25 Chisso Corporation Varnish composition

Non-Patent Citations (4)

* Cited by examiner, † Cited by third party
Title
D. R. Dodds et al.; Journal of The Chemical Society, No. 18, Sep. 15, 1982. See PCT search report.
J. B. Jones et al.; Canada Journal of Chemistry, vol. 65, No. 10, pp. 2397-2404, 1987. See PCT search report.
Principles of Organic Synthesis, 3<SUP>rd </SUP>Edition, 640-643, 1993.
Wolfgang Sucrow et al. "Flüssig-kristalline 2-Cyclohexyldecaline"; Chemische Berichte, Verlag Chemie CMBH; vol. 118, No. 8, 1985, pp. 3350-3356.

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